CN104335357A - Multi-layer back electrode for a photovoltaic thin-film solar cell, use of the same for producing thin-film solar cells and modules, photovoltaic thin-film solar cells and modules containing the multi-layer back electrode and method for the production thereof - Google Patents

Multi-layer back electrode for a photovoltaic thin-film solar cell, use of the same for producing thin-film solar cells and modules, photovoltaic thin-film solar cells and modules containing the multi-layer back electrode and method for the production thereof Download PDF

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CN104335357A
CN104335357A CN201380028772.XA CN201380028772A CN104335357A CN 104335357 A CN104335357 A CN 104335357A CN 201380028772 A CN201380028772 A CN 201380028772A CN 104335357 A CN104335357 A CN 104335357A
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layer
thin
back electrode
metal
molybdenum
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V.普罗布斯特
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Nice Solar Energy GmbH
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Robert Bosch GmbH
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    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
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    • H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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Abstract

The invention relates to a multi-layer back electrode for a photovoltaic thin-film solar cell, comprising, in this order, at least one bulk back electrode layer, containing or substantially consisting of V, Mn, Cr, Mo, Co, Zr, Ta, Nb and/or W and/or containing or substantially consisting of alloys containing V, Mn, Cr, Mo, Co, Zr, Fe, Ni, Al, Ta, Nb and/or W; at least one conductive barrier layer; at least one, in particular ohmic contact layer, containing or substantially consisting of Mo, W, Ta, Nb, Zr and/or Co, in particular Mo and/or W, and/or containing or substantially consisting of at least one metal chalcogenide, and/or containing at least one first layer, adjacent to the barrier layer, containing or substantially consisting of Mo, W, Ta, Nb, Zr and/or Co, in particular Mo and/or W, and at least one second layer which is non-adjacent to the barrier layer, containing or substantially consisting of at least one metal chalcogenide.

Description

Multilayer back electrode for photovoltaic thin-layer solar cell, the application of the multilayer back electrode for the manufacture of thin-layer solar cell and thin-layer solar module, the photovoltaic thin-layer solar cell comprising multilayer back electrode and module and manufacture method
Technical field
The present invention relates to the multilayer back electrode for photovoltaic thin-layer solar cell, the multilayer back electrode for the manufacture of thin-layer solar cell and thin-layer solar module application, comprise according to the photovoltaic thin-layer solar cell of multilayer back electrode of the present invention and module and the method for the manufacture of photovoltaic thin-layer solar cell and module.
Background technology
That suitable photovoltaic solar cell comprises crystal on the one hand and unbodied silicon solar module and comprise so-called thin-layer solar module on the other hand.General IB-IIIA-VIA-compound semiconductor layer, i.e. so-called chalcopyrite-semiconductor absorption layer in the latter cases.Usually molybdenum dorsum electrode layer is applied on a glass substrate in these thin-layer solar modules.In a kind of method flexible program, this molybdenum dorsum electrode layer is provided with copper and indium and is provided with the Driving Metal thin layer that comprises gallium if desired and then changes into so-called CIS or CIGS system at elevated temperatures when there is hydrogen sulfide and/or hydrogen selenide.
In order to reliably realize acceptable efficiency, usually just require to pay special attention to when selecting and manufacture dorsum electrode layer.Such as, dorsum electrode layer has high transverse conduction, to ensure the Series Wiring that loss is few.The material moved from substrate and/or semiconductor absorption layer also should not have an impact to the quality of dorsum electrode layer and envelop of function.In addition, the material of dorsum electrode layer must have substrate and the good conformity of hot stretched characteristic being in the layer on substrate, to avoid micro-crack.Finally, adhesiveness on the surface of a substrate also should meet all common instructions for uses.
Although can reach good efficiency by using back electrode material pure especially, incident is usually disproportionately high production cost.In addition, aforesaid migration or especially diffusion phenomena little obvious pollution not causing back electrode material under common working condition.
According to DE 44 42 824 C1, the absorbed layer with form favourable structure and high efficiency solar cell should be realized in the following way: chalcopyrite-semiconductor absorption layer is selected from element in the group of sodium, potassium and lithium with 10 14to 10 16atom/cm 2dosage adulterate and simultaneously diffusion impervious layer be set between substrate and semiconductor absorption layer.Instead, if should abandon diffusion impervious layer, then suggestion uses the substrate of alkali-free.
People (the Thin Solid Films 2011) suggestions such as Bl sch: use the layer system be made up of titanium, titanium nitride and molybdenum when using polyimide substrate film, to obtain good adhesion characteristics and gratifying thermal characteristics overview.People's (IEEE, the 2011,1st volume, No. 2, the 194 to 199 page) such as Bl sch also advise using stainless steel lining counterdie to use flexible thin-layer solar cell, and first this stainless steel lining counterdie applies thin titanium layer for improving adhesiveness.Utilize this CIGS thin-layer solar cell being equipped with titanium/triple coating of molybdenum/molybdenum to realize gratifying result.Also the technology of WO 2011/123869 A2 is utilized to instruct the thin-layer solar cell of making every effort to improvement.The disclosed solar cell layer that comprises soda-lime glass substrate, molybdenum dorsum electrode layer, cigs layer, resilient coating, the layer be made up of intrinsic zinc oxide and be made up of the zinc oxide adulterated with aluminium in the publication.First is separated groove extends on molybdenum layer, cigs layer and powder bed, and second is separated groove starts above molybdenum layer.Insulating material first to be separated in groove or on be deposited, and front electrode layer is deposited on solar cell (comprising the first separation groove) obliquely.The thin-layer solar cell being with the light throughput be improved should be obtained in this way.US 2004/014419A1 makes every effort to provide a kind of thin-layer solar cell, and its molybdenum dorsum electrode layer has the efficiency of improvement.This should realize in the following way, is provided with the glass substrate of the dorsum electrode layer be made up of molybdenum, and the thickness of this dorsum electrode layer should be no more than 500nm.
At people there (Thin Solid Films such as Orgassa, 2003,431-432 rolls up, the 1987 to 1993 page) just have been found that the very different metal of consideration such as tungsten, molybdenum, chromium, tantalum, niobium, vanadium, titanium and manganese are used as the suitable back electrode material of thin-layer solar cell.
Summary of the invention
Therefore, the present invention based on task be, be provided for the back electrode system of thin-layer solar cell or thin-layer solar module, its no longer have prior art shortcoming and especially with low cost and reliably the renewable place of production of mode cause with high efficiency thin-layer solar module.
Therefore, find a kind of multilayer back electrode for photovoltaic thin-layer solar cell or thin-layer solar module, comprise according to priority:
At least one block dorsum electrode layer (Bulk-R ü ckelektrodenschicht), comprise V, Mn, Cr, Mo, Co, Zr, Ta, Nb and/or W or be substantially made up of V, Mn, Cr, Mo, Co, Zr, Ta, Nb and/or W, and/or the alloy comprised containing V, Mn, Cr, Mo, Co, Zr, Fe, Ni, Al, Ta, Nb and/or W and/or be substantially made up of the alloy containing V, Mn, Cr, Mo, Co, Zr, Fe, Ni, Al, Ta, Nb and/or W;
At least one electrically conductive barrier;
The contact layer of at least one especially ohm,
Comprise Mo, W, Ta, Nb, Zr and/or Co or substantially by Mo, W, Ta, Nb, Zr and/or Co is formed, and especially comprises Mo and/or W or is substantially made up of Mo and/or W,
And/or
Comprise at least one metal chalcogenide or be substantially made up of at least one metal chalcogenide,
And/or
Comprise the first coating that at least one is adjacent with barrier layer, comprise Mo, W, Ta, Nb, Zr and/or Co or substantially by Mo, W, Ta, Nb, Zr and/or Co is formed, especially comprise Mo and/or W or be substantially made up of Mo and/or W, and at least one second coating, it is not adjacent with barrier layer, also be namely always separated with barrier layer by the first coating, comprise at least one metal chalcogenide or be substantially made up of at least one metal chalcogenide.
At this, specify in the preferred expansion scheme of one, block back electrode and contact layer comprise molybdenum or tungsten or molybdenum alloy or tungsten alloy, especially molybdenum or molybdenum alloy, or are substantially made up of molybdenum or tungsten or molybdenum alloy or tungsten alloy, are especially substantially made up of molybdenum or molybdenum alloy.
In addition can specify: barrier layer is for from the migration of block dorsum electrode layer, especially diffusion or diffusible composition and/or through the migration of block dorsum electrode layer, especially diffusion or the stop of diffusible composition, and/or be for from contact layer migration, especially diffusion or diffusible composition and/or the stop through contact layer migration, especially diffusion or diffusible composition.This barrier layer is preferably beidirectional stop therefore.Advantageously also specify within this context: barrier layer is the stop for basic ion, especially sodium ion, selenium or selenium compound, sulphur or sulphur compound, metal, especially Cu, In, Ga, Fe, Ni, Ti, Zr, Hf, V, Nb, Ta, Al and/or W and/or the compound containing basic ion such as sodium ion.Specify in the expansion scheme conforming with object especially: barrier layer comprises at least one metal nitride especially TiN, MoN, TaN, ZrN and/or WN, at least one metal carbides, at least one metal boride and/or at least one metal silicon nitride especially TiSiN, TaSiN and/or WSiN or substantially by least one metal nitride especially TiN, MoN, TaN, ZrN and/or WN, at least one metal carbides, at least one metal boride and/or at least one metal silicon nitride especially TiSiN, TaSiN and/or WSiN is formed.Preferably, the metal of metal nitride, metal silicon nitride, metal carbides and/or metal boride is titanium, molybdenum, tantalum or tungsten.This metal nitride is preferred as barrier material in the sense of the present invention, such as TiN, wherein this metal about nitrogen chemical metering or over-stoichiometric ground, be also namely deposited with excessive nitrogen.
As beidirectional barrier layer, the barrier layer of conduction is moved for from dorsum electrode layer, especially diffusion or diffusible composition (especially dopant) and/or move through dorsum electrode layer, especially the stop of diffusion or diffusible composition (especially dopant), and be move for from contact layer (being especially made up of semiconductor absorption layer), especially diffusion or diffusible composition (especially dopant) and/or move through contact layer (being especially made up of semiconductor absorption layer), especially the stop of diffusion or diffusible composition (especially dopant).Ground is determined, such as, it is likely that significantly reduce the purity of block back electrode material by the situation that there is barrier layer.Such as block dorsum electrode layer may be selected from the element of the group be made up of following element by least one: the compound of Fe, Ni, Ti, Zr, Hf, V, Nb, Ta, Al, W and/or Na and/or above-mentioned element pollute, and can not adversely affect there is the thin-layer solar cell of back electrode of the present invention or the efficiency of module.
When being used in thin-layer solar cell and module, the additional advantage on the barrier layer with multilayer back electrode of the present invention is used to show: the thickness that obviously can reduce semiconductor absorption layer, such as brass ore bed or kesterite layer relative to legacy system.Because by barrier layer (especially depositing in case with metal nitride such as titanium nitride form or the form that comprises this metal nitride or titanium nitride), sunlight through semiconductor absorption layer is effectively reflected, and makes can realize extraordinary quantum throughput on the dual path penetrating semiconductor absorption layer.Due in back electrode of the present invention or comprise in the thin-layer solar cell of described back electrode or module and there is described barrier layer, the average thickness of semiconductor absorption layer can be reduced to the value such as in 0.4 μm to 1.5 μm scope, such as, be reduced to the value in 0.5 μm to 1.2 μm scope.
Conform with especially in the expansion scheme of object a kind of, the barrier layer of back electrode of the present invention have for dopant especially for for semiconductor absorption layer and/or from semiconductor absorption layer dopant, for chalcogen as selenium and/or sulphur and chalcogenide compound, for semiconductor absorption layer metal part as Cu, In, Ga, Sn and/or Zn, for the pollutant from block dorsum electrode layer as iron and/or nickel and/or for from the composition of substrate and/or the barrier properties of pollutant, especially bidirectional obstruction characteristic.Should prevent from the one hand gathering basic ion, such as, from the basic ion that glass substrate diffuses out on the interface of back electrode or contact layer and semiconductor absorption layer for the bidirectional obstruction characteristic of the dopant from substrate.Thisly to gather as carrying out the reason of semiconductor layer dissolving and known.Therefore the barrier layer of conduction should help avoid sticking problem.On the other hand, barrier properties should for from semiconductor absorber diffusion or preventing from the dopant that semiconductor absorber diffuses out: dopant loses towards block back electrode in this way and makes the dopant of semiconductor absorber reduce thus, and this can the efficiency of obviously minimizing solar cell or solar energy module.Because such as it is known that molybdenum back electrode can absorb a large amount of natrium doping agent.Therefore two-way electrically conductive barrier should realize the precondition for dopant autotelic doping in semiconductor absorption layer, can realize the high efficiency of solar cell and solar energy module renewablely.
Barrier properties for chalcogen should prevent: chalcogen arrives back electrode and forms metal chalcogenide compounds there.Knownly, these chalcogenide compound (such as MoSe) cause the obvious volume of the near surface layer of back electrode to increase, and this brings again the unevenness of Rotating fields and the adhesiveness of variation.The pollutant of block back electrode material is the so-called dark impurity (semiconductor poisons) of chalcopyrite semiconductor as Fe and Ni and therefore it will be kept away from semiconductor absorption layer via barrier layer.
In addition, can specify in one embodiment, contact layer or the metal of metal chalcogenide of the second coating of contact layer is selected from molybdenum, tungsten, tantalum, zirconium, cobalt and/or niobium and the chalcogen of metal chalcogenide is selected from selenium and/or sulphur, wherein metal chalcogenide especially MSe 2, MS 2and/or M(Se 1-x, S x) 2, M=Mo, W, Ta, Zr, Co or Nb, wherein x gets the arbitrary value of 0 to 1.Preferably, metal chalcogenide is selected from MoSe 2, WSe 2, TaSe 2, NbSe 2, Mo(Se 1-x, S x) 2, W(Se 1-x, S x) 2, Ta(Se 1-x, S x) 2and/or Nb(Se 1-x, S x) 2the group formed, wherein x gets the arbitrary value of 0 to 1.
Further preferably, the metal of the first coating of the metal of the first coating of contact layer and/or contact layer consistent with the metal of the second coating and/or the metal of the second coating consistent with the metal of block back electrode.
Particularly advantageous this according to back electrode of the present invention as follows in addition, wherein the first and/or second coating of contact layer, contact layer has the dopant of at least one for the semiconductor absorption layer of thin-layer solar cell, especially there is the element that at least one is selected from following group: at least one compound of sodium, potassium and lithium and/or these elements, preferably with aerobic, selenium, sulphur, boron and/or halogen such as iodine or fluorine, and/or there is at least one alkali metal bronze, especially bronze sodium and/or bronze potassium, preferably with the metal being selected from molybdenum, tungsten, tantalum and/or niobium.The mixture that suitable bronze comprises mixed oxide or is made up of mixed oxide and oxide, such as Na 2moO 2+ WO.The contact layer of doping such as can be obtained by the metal chalcogenide applying the dopant be mixed with in metal chalcogenide source.
Preferably specify in the sense of the present invention: the average thickness of block dorsum electrode layer is in the scope of 50nm to 500nm, especially in the scope of 80nm to 250nm, and/or the average thickness on barrier layer is in the scope of 10nm to 250nm, especially in the scope of 20nm to 150nm, and/or the average thickness of contact layer is in the scope of 2nm to 200nm, especially in the scope of 5nm to 100nm.Thus preferably the gross thickness of multilayer back electrode should be set as making the all-in resistance rate of back electrode of the present invention to be no more than 50 microhm * cm, preferably more than 10 microhm * cm at this.Under these regulations, reduce the ohmic loss in serial module structure again.
Specify in the expansion scheme conforming with object especially: block dorsum electrode layer comprises molybdenum and/or tungsten, especially molybdenum, or be substantially made up of molybdenum and/or tungsten, especially molybdenum, the barrier layer of conduction comprises TiN or is substantially made up of TiN, and the contact layer especially comprising (one or more) dopant comprises MoSe 2or substantially by MoSe 2form.
Be proved to be as conforming with object, the dopant (especially sodium ion) in the semiconductor absorption layer of the thin-layer solar cell or module with back electrode and/or in contact layer is in 10 on dosage 13to 10 17atom/cm 2scope in, preferably on dosage, be in 10 14to 10 16atom/cm 2scope in.
For the situation of adulterating to contact layer with the dopant of the semiconductor absorption layer for thin-layer solar cell, the multilayer back electrode back of the body of the present invention is proved to be feasible.When manufacturing semiconductor absorption layer, often use higher than 300 DEG C or higher than the temperature of 350 DEG C.Usually, these temperature are also in the scope of 500 DEG C to 600 DEG C.Under this temperature conditions, dopant (in particular, for example sodium ion or sodium compound) moves from the contact layer of doping, is especially diffused into semiconductor absorption layer.Due to barrier layer, do not occur to the migration in dorsum electrode layer or diffusion.
Due to process semiconductor time described in relatively high temperature, advantageously: the layer selected of multilayer back electrode, the especially barrier layer of block back electrode and/or conduction are combined together, its thermal linear expansion coefficient is made to adapt to the thermal linear expansion coefficient of semiconductor absorber and/or substrate.Therefore, block back electrode and/or the barrier layer of thin-layer solar cell especially of the present invention and thin-layer solar module are preferably combined together, make thermal linear expansion coefficient be no more than 14*10 -6-k, preferably more than 9*10 -6-k.
The present invention based on task solved by the photovoltaic thin-layer solar cell and module that comprise multilayer back electrode of the present invention equally.
In the preferred expansion scheme of one, thin-layer solar cell of the present invention has at least one substrate layer, at least one dorsum electrode layer of the present invention, the barrier layer of at least one conduction, at least one especially direct setting semiconductor absorption layer on the contact layer, especially chalcopyrite semiconductor absorbed layer or kesterite semiconductor absorption layer and electrode before at least one according to priority.
In the case, this thin-layer solar cell or module are favourable, have between semiconductor absorption layer and front electrode wherein at least one resilient coating (also claiming the first resilient coating), especially at least one comprise CdS or the layer be substantially made up of CdS or without CdS layer, especially comprise Zn(S, OH) or In 2s 3or substantially by Zn(S, OH) or In 2s 3form, and/or at least one layer (also claiming the second resilient coating), it comprises the zinc oxide of intrinsic zinc oxide and/or high ohm or is substantially made up of the zinc oxide of intrinsic zinc oxide and/or high ohm.
Following this thin-layer solar cell of the present invention is also proved to be and conforms with object especially: semiconductor absorption layer is or comprises IB-IIIA-VIA-brass ore bed especially Cu (In, the Ga) Se of quaternary wherein 2layer, IB-IIIA-VIA-brass ore bed especially Cu (In, the Ga) (Se of five yuan 1-x, S x) 2layer or kesterite layer especially Cu 2znSn (Se x, S 1-x) 4layer, wherein x gets the arbitrary value of 0 to 1.Kesterite layer is usually based on IB-IIA-IVA-VIA structure.Exemplarily there is Cu 2znSnSe 4and Cu 2znSnS 4.
The average thickness of semiconductor absorption layer is in the scope of 400nm to 2500nm usually, to be especially in the scope of 500nm to 1500nm and to be preferably in the scope of 800nm to 1200nm.
At least two, especially a large amount of especially single chip integrated thin-layer solar cell of the present invention be connected in series is comprised according to photovoltaic thin-layer solar module of the present invention.Such as, in thin-layer solar module of the present invention, there are 20 to 150 or 50 to 100 thin-layer solar cells of the present invention be connected in series.
In a kind of suitable expansion scheme, the all-in resistance rate of multilayer back electrode of the present invention should be no more than 50 microhm * cm, preferably more than 10 microhm * cm.Low-loss as far as possible, single chip integrated being connected in series should be able to be ensured in this way.
The present invention based on task solved by the method for the manufacture of photovoltaic thin-layer solar cell of the present invention or photovoltaic thin-layer solar module of the present invention in addition, comprise step:
Block dorsum electrode layer is applied by physics thin layer deposition method or by chemical vapor deposition, barrier layer, contact layer, the metal of semiconductor absorption layer and/or one or more dopants, described physics thin layer deposition method especially comprises physical vapor deposition (PVD) coating, by the evaporation of electron-beam evaporator, by thermal resistance evaporation device, inductance evaporates, the evaporation of ARC evaporation and/or negative electrode spraying (splash coating) especially DC or RF magnetron sputtering, these evaporations preferably carry out respectively in high vacuum, described chemical vapor deposition especially comprises chemical vapor deposition (CVD), low pressure (low pressure) CVD and/or atmospheric pressure (atmospheric pressure) CVD.
In the case, this execution mode is favourable, and wherein the metal of block dorsum electrode layer, barrier layer, contact layer, semiconductor absorption layer and/or one or more dopants apply by negative electrode spraying (splash coating) especially DC magnetron sputtering.
Here can also specify, one or more dopants especially apply from common mixing or sintering target together with at least one composition of contact layer and/or absorbed layer.Finally, be also proved and conform with object, mixing or sintering target comprise at least one dopant, and it is selected from sodium compound, sodium molybdenum bronze and sodium tungsten bronze, is especially being selected from MoSe 2, WSe 2, Mo, W, copper and/or gallium matrix components in.Such as, selenizing molybdenum target can be mixed with sodium sulfite as dopant or vulcanized sodium.
The present invention is utilized to bring mirable discovery: the structure of multilayer back electrode of the present invention can be utilized to realize the semiconductor absorption layer thickness of the relative thin in thin-layer solar cell or module, and need not take loss in efficiency as cost.Utilize system of the present invention, usually even occur higher efficiency.Find thus: the barrier layer of reflected sunlight contributes to further electric current and produces.Sunlight here twice through semiconductor absorption layer.Find: the efficiency also bringing improvement in the following manner, namely semiconductor absorption layer (such as based on chalcopyrite or kesterite system) is directly deposited on molybdenum contact layer also marvellously.In the case, this semiconductor absorption layer can react and generate selenizing molybdenum or sulphur selenizing molybdenum in semiconductor forming process then on interface.In addition, find: the dopant (such as based on sodium) for semiconductor absorption layer according to dosage properly enters into described semiconductor absorption layer by contact layer (being also original being present in contact layer) also marvellously.For this reason, enough, wherein barrier layer is auxiliarily related affects the migratory direction of dopant to semiconductor absorption layer direction to the temperature when forming semiconductor absorption layer.As long as exist in semiconductor absorption layer, described dopant contributes to the efficiency improving thin-layer solar cell or module usually.Be proved to be advantageously in the case, by the last amount being present in the dopant in semiconductor absorption layer in the product made very accurately can be set through entering of contact layer.The reproducible efficiency that just component of realization and glass and/or block back electrode is irrelevant in this way improves.Utilize present system, the loss in efficiency caused due to the not controlled reaction of chalcogen, especially selenium during forming the semiconductor absorption layer with block back electrode can also be avoided marvellously.By no longer forming metal chalcogenide as selenizing molybdenum on the surface of block back electrode, also avoiding the conductivity of block back electrode to lose and avoid the chalkogenide of transversal inhomogeneity to be formed and prevent the formation of micro-crack thus.Because along with the formation of chalkogenide there will be disadvantageous volumetric expansion usually.Utilize system of the present invention, such as, can more accurately and more reliably set the thickness of each layer and the thickness of total system than in traditional thin-layer system situation.Multilayer back electrode of the present invention allows to use contaminated piece of back electrode material simultaneously, and the efficiency of thin-layer solar cell can not affect adversely.Therefore, the total cost of thin-layer solar module can obviously reduce.In addition, multilayer back electrode of the present invention is utilized to carry out the obviously more controlled structure of semiconductor absorption layer.Part such as Cu, In and/or Ga of semiconductor no longer move in back electrode, on purpose can set the desired mass ratio of the composition forming semiconductor absorption layer thus and also can keep this mass ratio.
Accompanying drawing explanation
To obtain in other features and advantages of the present invention description from behind, exemplarily set forth by schematic diagram preferred embodiment of the present invention wherein.At this:
Fig. 1 illustrates the schematic cross-sectional view comprising the part system of the first execution mode of multilayer back electrode of the present invention of thin-layer solar cell;
Fig. 2 illustrates the schematic cross-sectional view comprising the part system of the second execution mode of multilayer back electrode of the present invention of thin-layer solar cell; And
Fig. 3 shows the schematic cross-sectional view comprising the part system of the 3rd execution mode of multilayer back electrode of the present invention of thin-layer solar cell.
Embodiment
In the execution mode of multilayer back electrode 1 of the present invention shown in Figure 1, substrate layer 2 such as glass substrate has the block dorsum electrode layer 4 be made up of molybdenum.The barrier layer 6 that this block dorsum electrode layer 4 has beidirectional to conduct electricity, barrier layer 6 is such as made up of tungsten nitride or titanium nitride, and has ohmic contact layer 8a that is adjacent with this layer, that be made up of as selenizing molybdenum metal chalcogenide.Also can be mixed with at least one dopant in a preferred embodiment at this this contact layer 8a, described dopant is such as sodium ion or sodium compound, especially sodium sulfite or vulcanized sodium.
In second execution mode of the multi-layered electrode of the present invention 1 reproduced in fig. 2, different from the execution mode according to Fig. 1, contact layer 8b is metal level, such as molybdenum layer or tungsten layer.This contact layer 8b also can be mixed with at least one dopant in preferred expansion scheme, such as, be mixed with sodium ion or sodium compound, especially sodium sulfite or vulcanized sodium.
In 3rd execution mode of the multi-layered electrode of the present invention 1 reproduced in figure 3, contact layer 8c is the two layer system that the first coating 10 by being made up of metal such as molybdenum or tungsten and the second coating 12 of being made up of metal chalcogenide such as selenizing molybdenum and/or tungsten selenide are formed, wherein the first coating and barrier layer 6 adjacent or adjacent with barrier layer 6, and metal chalcogenide and the first coating 10 adjoin and not adjacent with barrier layer 6 thus.In this embodiment, in contact layer 8c, preferably at least one dopant is also had, such as sodium ion or sodium compound, especially sodium sulfite or vulcanized sodium.In the case, this dopant can be added in the first and/or second coating.
In the foregoing description, in claim and in the accompanying drawings, disclosed feature of the present invention can individually and with combination in any for realization of the present invention in its various execution mode.

Claims (22)

1., for the multilayer back electrode of photovoltaic thin-layer solar cell, comprise according to priority:
At least one block dorsum electrode layer, comprise V, Mn, Cr, Mo, Co, Zr, Ta, Nb and/or W or be substantially made up of V, Mn, Cr, Mo, Co, Zr, Ta, Nb and/or W, and/or the alloy comprised containing V, Mn, Cr, Mo, Co, Zr, Fe, Ni, Al, Ta, Nb and/or W and/or be substantially made up of the alloy containing V, Mn, Cr, Mo, Co, Zr, Fe, Ni, Al, Ta, Nb and/or W;
At least one electrically conductive barrier;
The contact layer of at least one especially ohm,
Comprise Mo, W, Ta, Nb, Zr and/or Co or substantially by Mo, W, Ta, Nb, Zr and/or Co is formed, and especially comprises Mo and/or W or is substantially made up of Mo and/or W,
And/or
Comprise at least one metal chalcogenide or be substantially made up of at least one metal chalcogenide,
And/or
Comprise the first coating that at least one is adjacent with barrier layer, comprise Mo, W, Ta, Nb, Zr and/or Co or substantially by Mo, W, Ta, Nb, Zr and/or Co is formed, especially comprise Mo and/or W or be substantially made up of Mo and/or W, and at least one second not adjacent with barrier layer coating, comprise at least one metal chalcogenide or be substantially made up of at least one metal chalcogenide.
2. back electrode according to claim 1, it is characterized in that, block back electrode and contact layer comprise molybdenum or tungsten or molybdenum alloy or tungsten alloy, especially molybdenum or molybdenum alloy, or are substantially made up of molybdenum or tungsten or molybdenum alloy or tungsten alloy, are especially substantially made up of molybdenum or molybdenum alloy.
3. back electrode according to claim 1 and 2, it is characterized in that, barrier layer is for from the migration of block dorsum electrode layer, especially diffusion or diffusible composition and/or through the migration of block dorsum electrode layer, especially diffusion or the stop of diffusible composition, and/or is for from contact layer migration, especially diffusion or diffusible composition and/or the stop through contact layer migration, especially diffusion or diffusible composition.
4. according to the back electrode one of aforementioned claim Suo Shu, it is characterized in that, barrier layer is the stop for basic ion, especially sodium ion, selenium or selenium compound, sulphur or sulphur compound, metal especially Cu, In, Ga, Fe, Ni, Ti, Zr, Hf, V, Nb, Ta, Al and/or W and/or the compound containing basic ion.
5. according to the back electrode one of aforementioned claim Suo Shu, it is characterized in that, barrier layer comprises at least one metal nitride especially TiN, MoN, TaN, ZrN and/or WN, at least one metal carbides, at least one metal boride and/or at least one metal silicon nitride especially TiSiN, TaSiN and/or WSiN, or substantially by least one metal nitride especially TiN, MoN, TaN, ZrN and/or WN, at least one metal carbides, at least one metal boride and/or at least one metal silicon nitride especially TiSiN, TaSiN and/or WSiN is formed.
6. according to the back electrode one of aforementioned claim Suo Shu, it is characterized in that, block dorsum electrode layer is selected from the element of the group be made up of following element by least one: the compound of Fe, Ni, Ti, Zr, Hf, V, Nb, Ta, W, Al and/or Na and/or above-mentioned element pollute.
7. according to the back electrode one of aforementioned claim Suo Shu, it is characterized in that, contact layer or the metal of metal chalcogenide of the second coating of contact layer is selected from molybdenum, tungsten, tantalum, zirconium, cobalt and/or niobium and the chalcogen of this metal chalcogenide is selected from selenium and/or sulphur, wherein metal chalcogenide especially MSe 2, MS 2and/or M(Se 1-x, S x) 2, M=Mo, W, Ta, Zr, Co or Nb, wherein x gets the value of 0 to 1.
8., according to the back electrode one of aforementioned claim Suo Shu, it is characterized in that,
The metal of the first coating of contact layer is consistent with the metal of the second coating, and/or the metal of the first coating of contact layer and/or the metal of the second coating consistent with the metal of block back electrode.
9., according to the back electrode one of aforementioned claim Suo Shu, it is characterized in that,
First and/or second coating of contact layer, contact layer has the dopant of at least one for the semiconductor absorption layer of thin-layer solar cell, especially there is the element that at least one is selected from following group: at least one compound of sodium, potassium and lithium and/or these elements, preferably with aerobic, selenium, sulphur, boron and/or halogen such as iodine or fluorine, and/or there is at least one alkali metal bronze, especially bronze sodium and/or bronze potassium, preferably with the metal being selected from molybdenum, tungsten, tantalum and/or niobium.
10., according to the back electrode one of aforementioned claim Suo Shu, it is characterized in that,
The average thickness of block dorsum electrode layer is in the scope of 50nm to 500nm, especially in the scope of 80nm to 250nm, and/or the average thickness on barrier layer is in the scope of 10nm to 250nm, especially in the scope of 20nm to 150nm, and/or the average thickness of contact layer is in the scope of 2nm to 200nm, especially in the scope of 5nm to 100nm.
11., according to the back electrode one of aforementioned claim Suo Shu, is characterized in that,
Block dorsum electrode layer comprises molybdenum and/or tungsten especially molybdenum, or is substantially made up of molybdenum and/or tungsten especially molybdenum,
The barrier layer of conduction comprises TiN or is substantially made up of TiN, and
Especially the contact layer comprising one or more dopants comprises MoSe 2or substantially by MoSe 2form.
12., according to the back electrode one of claim 9 to 11 Suo Shu, is characterized in that, the dopant in contact layer, especially sodium ion are in 10 on dosage 13to 10 17atom/cm 2scope in, be especially in 10 14to 10 16atom/cm 2scope in.
13. photovoltaic thin-layer solar cells, comprise at least one according to the multilayer back electrode one of aforementioned claim Suo Shu.
14. thin-layer solar cells according to claim 13, comprise at least one substrate layer, at least one barrier layer according to the dorsum electrode layer one of the claims in the present invention 1 to 12 Suo Shu, at least one conduction, at least one especially direct setting semiconductor absorption layer on the contact layer, especially chalcopyrite semiconductor absorbed layer or kesterite semiconductor absorption layer and electrode before at least one according to priority.
15. thin-layer solar cells according to claim 14, it is characterized in that, have between semiconductor absorption layer and front electrode at least one resilient coating, especially at least one comprise CdS or the layer be substantially made up of CdS or without CdS layer, especially comprise Zn(S, OH) or In 2s 3or substantially by Zn(S, OH) or In 2s 3form, and/or at least one zinc oxide comprising intrinsic zinc oxide and/or high ohm or the layer be substantially made up of the zinc oxide of intrinsic zinc oxide and/or high ohm.
16., according to claim 13 to the thin-layer solar cell one of 15 described, is characterized in that,
Semiconductor absorption layer is or comprises IB-IIIA-VIA-brass ore bed especially Cu (In, the Ga) Se of quaternary 2layer, IB-IIIA-VIA-brass ore bed especially Cu (In, the Ga) (Se of five yuan 1-x, S x) 2layer or kesterite layer especially Cu 2znSn (Se x, S 1-x) 4layer, wherein x gets the value of 0 to 1, and/or the average thickness of semiconductor absorption layer is in the scope of 400nm to 2500nm, to be especially in the scope of 500nm to 1500nm and to be preferably in the scope of 800nm to 1200nm.
17. photovoltaic thin-layer solar modules, comprise at least two, especially a large amount of especially single chip integrated be connected in series according to claim 13 to one of 16 described thin-layer solar cells.
18. according to claim 13 to the application of the thin-layer solar cell one of 16 described for the manufacture of photovoltaic thin-layer solar module.
19. according to the application of the multilayer back electrode one of claim 1 to 12 Suo Shu for the manufacture of thin-layer solar cell or thin-layer solar module.
20. are used for the application to semiconductor absorption layer doping during manufacturing especially according to claim 13 to the photovoltaic thin-layer solar cell one of 16 described or photovoltaic thin-layer solar module especially according to claim 17 according to the multilayer back electrode one of claim 9 to 12 Suo Shu.
21., for the manufacture of the method according to claim 13 to the photovoltaic thin-layer solar cell one of 16 described or photovoltaic thin-layer solar module according to claim 17, comprise step:
Block dorsum electrode layer is applied by physics thin layer deposition method or by chemical vapor deposition, barrier layer, contact layer, the metal of semiconductor absorption layer and/or one or more dopants, described physics thin layer deposition method especially comprises physical vapor deposition (PVD) coating, by the evaporation of electron-beam evaporator, by thermal resistance evaporation device, inductance evaporates, the evaporation of ARC evaporation and/or negative electrode spraying (splash coating) especially DC or RF magnetron sputtering, these evaporations preferably carry out respectively in high vacuum, described chemical vapor deposition especially comprises chemical vapor deposition (CVD), low pressure (low pressure) CVD and/or atmospheric pressure (atmospheric pressure) CVD.
22. methods according to claim 20 or 21, it is characterized in that, one or more dopants being especially selected from sodium compound, sodium ion, sodium molybdenum bronze and/or sodium tungsten bronze are applied in together with at least one composition of contact layer and/or absorbed layer, are especially applied in from common mixing or sintering target.
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